EP1178951B1 - Eta 5-phospholyl complexes and their use in hydroformylation - Google Patents

Eta 5-phospholyl complexes and their use in hydroformylation Download PDF

Info

Publication number
EP1178951B1
EP1178951B1 EP00935014A EP00935014A EP1178951B1 EP 1178951 B1 EP1178951 B1 EP 1178951B1 EP 00935014 A EP00935014 A EP 00935014A EP 00935014 A EP00935014 A EP 00935014A EP 1178951 B1 EP1178951 B1 EP 1178951B1
Authority
EP
European Patent Office
Prior art keywords
complex
mmol
hydroformylation
phospholyl
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00935014A
Other languages
German (de)
French (fr)
Other versions
EP1178951A1 (en
Inventor
Wolfgang Ahlers
Thomas Mackewitz
Michael Röper
François Mathey
Christian Ganter
Bernhard Breit
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1178951A1 publication Critical patent/EP1178951A1/en
Application granted granted Critical
Publication of EP1178951B1 publication Critical patent/EP1178951B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2438—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member and further hetero atoms as ring members, excluding the positions adjacent to P
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/2466—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • B01J2531/023—Phospholyl ligands, i.e. [CnP(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • the present invention relates to the use of ⁇ 5 -phospholyl complexes in complexes of transition metals of subgroup VIII.
  • Subgroup of the Periodic Table of the Elements in the production of aldehydes by hydroformylation of olefins with CO / H 2 at temperatures up to 200 ° C. and pressures up to 700 bar.
  • Rhodium-containing phosphine-modified catalysts have been used in particular for Hydroformylation of low-boiling olefins is of paramount importance won.
  • Rhodium-containing phosphite-modified catalysts have recently been proposed for the hydroformylation of low-boiling olefins (see M. Beller, B. Cornils, CD Frohning, CW Kohlpaintner, J. Mol. Catal 1995 , 104, 17). Both ⁇ -olefins and short-chain internal olefins such as 2-butene or 3-pentenoic acid methyl ester can be hydroformylated very well with rhodium-containing chelate-phosphite-modified catalysts. However, this catalyst system is not very suitable for long-chain internal olefins with more than 7 carbon atoms and internal, branched olefins. Monodentate, sterically hindered monophosphites have proven themselves experimentally for these olefins. However, phosphites generally have the disadvantage of sensitivity to hydrolysis and a tendency towards degradation reactions, which limits their technical use.
  • the present invention was therefore based on the object, new, against Hydrolysis and degradation-insensitive ligands, which as Cocatalysts for the transition metals of subgroup VIII, especially rhodium, catalyzed hydroformylation of olefins in particular are suitable, as well as a process for the preparation of aldehydes from ⁇ -olefins as well as from internal and / or branched olefins or from higher-boiling ones To provide olefins (with more than 7 carbon atoms).
  • the object is thus achieved by a process for the preparation of aldehydes by hydroformylation of olefins with CO / H 2 in the presence of complexes of transition metals of subgroup VIII of the periodic table of the elements at temperatures from 20 to 200 ° C. and pressures from atmospheric pressure to 700 bar , where catalysts with ⁇ 5 -phospholyl complexes capable of complex formation are used as ligands.
  • the transition metal ( ⁇ 1 metal) is rhodium.
  • the ⁇ 5 -phospholyl complexes are selected from the general structures I and V.
  • R 1 to R 4 independently of one another denote hydrogen, C 1-12 alkyl, C 7-12 aralkyl, C 7-12 alkaryl or C 6-12 aryl radicals or for the radicals COO - M + , SO 3 - M + , NR 3 + X - , OR, NR 2 , COOR, SR, (CHRCH 2 O) x R, (CH 2 NR) x R or (CH 2 CH 2 NR) x R, where R in each case the same or different radicals selected from hydrogen, C 1-12 alkyl and C 6-12 aryl radicals, M + is a cation and X - is an anion and x is the number from 1 to 120 and where the radicals R 1 to R 4 can be linked to fused rings, and in which ML n stands for a metal complex fragment and W is a bridge in the form of a covalent bond or a chain
  • L is selected from cyclopentadienyl, CO, halogen and Phosphine and mixtures thereof.
  • At least one of the substituents R 1 to R 4 can have an additional, trivalent phosphorus group capable of coordination, which results in a bidentate or multidentate ligand.
  • Phosphane, phosphinite, phosphonite or phosphabenzene groups are particularly preferred.
  • a nitrogen grouping, preferably pyridine grouping, can also be present.
  • Cy means Cyclohexyl, Ph phenyl.
  • WO 98/50392 (“Process to Prepare Bridged Phosphole-Cyclopentadienyl Compounds ”) describes the synthesis of phospholes and Phospholyl complexes and their use as polymerization catalysts.
  • the catalyst is preferably used for hydroformylation used by olefins.
  • the active carbonyl complex is usually in situ, i.e. in the hydroformylation reactor, from a salt or a compound the metal M ', the ligand and carbon monoxide; but he can also are manufactured and used separately.
  • complex catalysts are generated in situ, simple ones are used Precursor complexes such as rhodium dicarbonyl acetylacetonate or rhodium acetate in Presence of the corresponding ligands from the reaction conditions, or activator additives such as Brönsted or are added to precursor complexes Lewis acids or Lewis bases.
  • Precursor complexes such as rhodium dicarbonyl acetylacetonate or rhodium acetate in Presence of the corresponding ligands from the reaction conditions, or activator additives such as Brönsted or are added to precursor complexes Lewis acids or Lewis bases.
  • the Ligands in a molar ratio (calculated as equivalent phosphorus) Rhodium of preferably 1: 1 to 1000: 1.
  • An inert one is preferred Solvent used.
  • Particularly preferred solvents are Aldehydes, which are formed by the reaction of the respective olefin, and the High boilers in the synthesis, which are caused by subsequent reactions of the respective aldehyde arise in the hydroformylation process.
  • Hydrophilized ligands are preferably water, alcohols or others Solvent used.
  • composition of the synthesis gas CO / H 2 used in the hydroformylation process according to the invention can be varied within wide limits.
  • synthesis gas with CO / H 2 molar ratios from 5:95 to 70:30 can be used successfully, synthesis gas with CO / H 2 ratios from 40:60 to 60:40 is preferred, and CO / H 2 - is particularly preferred. Ratio of about 1: 1 applied.
  • Hydroformylation reactions with the catalysts described above preferably at a temperature of 20 to 200 ° C, especially at 50 to 150 ° C.
  • the reaction pressure can ever for cocatalyst and substrate in a range from normal pressure to 700 bar, preferably up to 300 bar, which are usually reactions in one Range up to about 30 bar as a low pressure and in a range up to about 100 bar as medium pressure and over 100 bar as high pressure reactions.
  • Suitable olefins to be hydroformylated according to the invention are ⁇ -olefins or internal olefins or internal, branched olefins. Functional groups are also tolerated.
  • the following olefins are mentioned by way of example: ethylene, propene, 1-butene, 1-octene, C 5-20 ⁇ -olefins, linear C 5-20 internal olefins, 2-butene, branched internal octene mixtures, branched internal non-mixtures, branched internal dodecene mixtures, cyclohexene, styrene, 3-pentenenitrile, 4-pentenenitrile, 3-pentenoic acid alkyl ester, 4-pentenoic acid alkyl ester, polypropene, polyisobutylene.
  • suitable substrates are di- or polyenes with isolated or conjugated double bonds.
  • suitable substrates are 1,3-butadiene, 1,5-hexadiene, vinylcyclohexene, dicylopentadiene, 1,5,9-cyclooctatriene, butadiene homo- and copolymers and polyisobutene.
  • Variant A Rhodium precursor, ligand and solvent were mixed in a Schlenk tube under nitrogen inert gas. The solution obtained was transferred to a 70 ml or 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to the desired temperature within 30 min. The olefin used was then pressed into the autoclave with CO / H 2 overpressure via a lock. The desired reaction pressure was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor.
  • Variant B Rhodium precursor, ligand and solvent were mixed under nitrogen inert gas in a Schlenk tube. The solution obtained was transferred to a 70 ml or 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. The reaction mixture was heated to 100 ° C. in the course of 30 min with vigorous stirring using a gassing stirrer. After the catalyst had been preformed, the autoclave was cooled and let down. The olefin used was then pressed into the autoclave with CO / H 2 overpressure via a lock. The reaction mixture was reheated to the desired temperature within 30 minutes.
  • the desired reaction pressure was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor.
  • the aldehydes in the reaction mixture of Example 5 were distilled off at 100 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the reaction's own high boilers. For this purpose, 6.8 g (61 mmol) of 1-octene were added in the absence of air. The solution obtained was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring with a gassing stirrer, the reaction mixture was heated to 90 ° C. within 30 minutes. A reaction pressure of 40 bar CO / H 2 was then immediately set using CO / H 2 (1: 1).
  • the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time of 4 h, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor. The 1-octene conversion was 67%, the yield of nonanals was 57%, the selectivity to n-nonanal (n component) was 73%, and the selectivity to n-nonanal and 2-methyloctanal ( ⁇ component) 100%.
  • a 31 P-NMR spectrum of the reaction discharge shows the unchanged presence of the cocatalyst within the scope of the measurement accuracy.
  • the aldehydes in the reaction mixture of Example 9 were distilled off at 100 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the company's own high boilers. To this end, 6.7 g (60 mmol) of 1-octene were added in the absence of air. The solution obtained was transferred to a 70 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 2 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to 90 ° C. within 30 minutes. The desired reaction pressure was then immediately set using CO / H 2 (1: 1).
  • the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time of 4 h, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor. The 1-octene conversion was 99%, the yield of nonanals was 32%, the selectivity to n-nonanal (n component) was 55%, and the selectivity to n-nonanal and 2-methyloctanal ( ⁇ component) 90%.
  • the aldehydes in the reaction mixture of Example 11 were distilled off at 100 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the reaction's own high boilers. 6.0 g (23 mmol) of 1-octene were added to this in the absence of air. The solution obtained was transferred to a 70 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to 90 ° C. within 30 minutes. A reaction pressure of 40 bar CO / H 2 was then immediately set using CO / H 2 (1: 1).
  • the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time of 4 h, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor. The 1-octene conversion was 100%, the yield of nonanals was 92%, the selectivity to n-nonanal (n component) was 26% and the selectivity to n-nonanal and 2-methyloctanal ( ⁇ component) was 65 %. A 31 P-NMR spectrum of the reaction output showed the unchanged presence of the cocatalyst within the scope of the measurement accuracy.
  • the aldehydes in the reaction mixture of Example 13 were distilled off at 70 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the reaction's own high boilers. The solution was transferred to a 70 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 4.5 g (80 mmol) of trans-2-butene with CO / H 2 overpressure were then pressed into the autoclave via a lock. The reaction mixture was heated to 100 ° C. in the course of 30 min with vigorous stirring using a gassing stirrer.
  • reaction pressure of 40 bar (intrinsic pressure of the olefin and CO / H 2 ) was then immediately set using CO / H 2 (1: 1).
  • the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator.
  • the autoclave was cooled, decompressed and emptied.
  • the reaction mixture was analyzed by GC with an internal standard and correction factor.
  • the trans-2-butene conversion was 65%, the yield of nonanals was 65%, and the selectivity to n-pentanal (n component) was 35%.
  • a 31 P-NMR spectrum of the reaction discharge showed the almost unchanged presence of the cocatalyst within the scope of the measurement accuracy.
  • the aldehydes in the reaction mixture of Example 15 were distilled off at 100 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the reaction's own high boilers.
  • the solution was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1).
  • 10.0 g (89 mmol) of octene-N2 were added in the absence of air.
  • the solution obtained was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold.
  • reaction mixture was heated to 90 ° C. within 30 minutes.
  • a reaction pressure of 60 bar CO / H 2 was then immediately set using CO / H 2 (1: 1).
  • the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator.
  • the autoclave was cooled, decompressed and emptied.
  • the reaction mixture was analyzed by GC with an internal standard and correction factor.
  • the octene-N2 conversion was 60% after 4 h reaction time and 88% after 24 h reaction time.
  • the yield of nonanals was 60% after 4 h reaction time and 88% after 24 h reaction time.
  • a 31 P-NMR spectrum of the reaction discharge showed the almost unchanged presence of the cocatalyst within the scope of the measurement accuracy.
  • the 1-octene conversion was 92%, the yield of nonanals was 83%, the selectivity to n-nonanal (n component) was 69% and the selectivity to n-nonanal and 2-methyloctanal ( ⁇ component) was 100 %.
  • the aldehydes in the reaction mixture of Example 19 were distilled off at 70 ° C under vacuum. What remained was a homogeneous solution consisting of an active catalyst, toluene and high-boilers from the reaction, which was supplemented with toluene to a total amount of 15 g.
  • the solution obtained was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 20 bar CO / H 2 (1: 1) were pressed in cold.
  • the reaction mixture was heated to 80 ° C. in the course of 30 minutes with vigorous stirring using a gassing stirrer. After the catalyst had been preformed, the autoclave was cooled and let down.
  • Rh (CO) 2 acac 0.7 mg (0.003 mmol) Rh (CO) 2 acac were initially charged with 3 g xylene and 17.8 mg (0.026 mmol) ligand and preformed for 30 min at 100 ° C. and 15 bar synthesis gas. 1.5 g (18.5 mmol) of 3-pentenenitrile were then injected and the pressure was adjusted to 15 bar. After a reaction time of 4 h, an aldehyde yield of 69% was achieved with a conversion of 71%. The linearity was 2%, the ⁇ portion was 26%.
  • Rh (CO) 2 acac 0.7 mg (0.003 mmol) Rh (CO) 2 acac were initially charged with 3 g xylene and 17.8 mg (0.026 mmol) ligand and preformed for 30 min at 100 ° C. and 15 bar synthesis gas. 1.5 g (18.5 mmol) of 4-pentenenitrile were then injected and the pressure was adjusted to 15 bar. After a reaction time of 4 h, an aldehyde yield of 42% was achieved with a conversion of 42%. The linearity was 52%, the ⁇ portion 100%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Die vorliegende Erfindung betrifft die Verwendung von η5-Phospholylkomplexen in Komplexen von Übergangsmetallen der VIII. Nebengruppe des Periodischen Systems der Elemente bei der Herstellung von Aldehyden durch Hydroformylierung von Olefinen mit CO/H2 bei Temperaturen bis 200°C und Drücken bis 700 bar.The present invention relates to the use of η 5 -phospholyl complexes in complexes of transition metals of subgroup VIII. Subgroup of the Periodic Table of the Elements in the production of aldehydes by hydroformylation of olefins with CO / H 2 at temperatures up to 200 ° C. and pressures up to 700 bar.

Jährlich werden weltweit etwa 7 Mio. Tonnen chemischer Produkte mit Hilfe der Hydroformylierung von Olefinen hergestellt. Es besteht deshalb ein großes wirtschaftliches Interesse daran, die Reaktion mit maximaler Selektivität und Aktivität zu betreiben.Every year, around 7 million tons of chemical products are processed worldwide using the Hydroformylation of olefins produced. So there is a big one economic interest in the reaction with maximum selectivity and Activity.

Rhodiumhaltige phosphanmodifizierte Katalysatoren haben insbesondere für die Hydroformylierung von niedersiedenden Olefinen eine überragende Bedeutung gewonnen.Rhodium-containing phosphine-modified catalysts have been used in particular for Hydroformylation of low-boiling olefins is of paramount importance won.

Zur Diskussion technischer Neuerungen wird auf M. Beller, B. Cornils, C. D. Frohning, C. W. Kohlpaintner, J. Mol. Catal. 1995, 104, 17 verwiesen. Obwohl α-Olefine sehr gut mit rhodiumhaitigen phosphanmodifizierten Katalysatoren hydroformylierbar sind, ist dieses Katalysatorsystem für interne und interne, verzweigte Olefine sowie für Olefine mit mehr als 7 Kohlenstoffatomen wenig geeignet. So werden interne Kohlenstoff-Kohlenstoff-Doppelbindungen nur sehr langsam in Gegenwart eines derartigen Katalysators hydroformyliert.For the discussion of technical innovations, M. Beller, B. Cornils, CD Frohning, CW Kohlpaintner, J. Mol. Catal. 1995, 104, 17. Although α-olefins can be hydroformylated very well with rhodium-containing phosphine-modified catalysts, this catalyst system is not very suitable for internal and internal, branched olefins and for olefins with more than 7 carbon atoms. Internal carbon-carbon double bonds are only hydroformylated very slowly in the presence of such a catalyst.

Rhodiumhaltige phosphitmodizifierte Katalysatoren werden neuerdings für die Hydroformylierung von niedersiedenden Olefinen vorgeschlagen (siehe M. Beller, B. Cornils, C. D. Frohning, C. W. Kohlpaintner, J. Mol. Catal 1995, 104, 17). Sowohl α-Olefine als auch kurzkettige interne Olefine wie 2-Buten oder 3-Pentensäuremethylester können sehr gut mit rhodiumhaltigen chelatphosphitmodifizierten Katalysatoren hydroformyliert werden. Allerdings ist dieses Katalysatorsystem für langkettige interne Olefine mit mehr als 7 Kohlenstoffatomen und interne, verzweigte Olefine wenig geeignet. Für diese Olefine haben sich einzähnige, sterisch gehinderte Monophosphite experimentell bewährt. Allerdings weisen Phosphite generell den Nachteil der Hydrolyseempfindlichkeit und der Tendenz zu Abbaureaktionen auf, wodurch deren technischer Einsatz eingeschränkt wird.Rhodium-containing phosphite-modified catalysts have recently been proposed for the hydroformylation of low-boiling olefins (see M. Beller, B. Cornils, CD Frohning, CW Kohlpaintner, J. Mol. Catal 1995 , 104, 17). Both α-olefins and short-chain internal olefins such as 2-butene or 3-pentenoic acid methyl ester can be hydroformylated very well with rhodium-containing chelate-phosphite-modified catalysts. However, this catalyst system is not very suitable for long-chain internal olefins with more than 7 carbon atoms and internal, branched olefins. Monodentate, sterically hindered monophosphites have proven themselves experimentally for these olefins. However, phosphites generally have the disadvantage of sensitivity to hydrolysis and a tendency towards degradation reactions, which limits their technical use.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, neue, gegen Hydrolyse und Abbaureaktionen unempfindliche Liganden, welche als Cokatalysatoren für die durch Übergangsmetalle der VIII. Nebengruppe, insbesondere Rhodium, katalysierte Hydroformylierung von Olefinen besonders geeignet sind, sowie ein Verfahren zur Herstellung von Aldehyden aus α-Olefinen sowie aus internen und/oder verzweigten Olefinen oder aus höhersiedenden Olefinen (mit mehr als 7 Kohlenstoffatomen) bereitzustellen.The present invention was therefore based on the object, new, against Hydrolysis and degradation-insensitive ligands, which as Cocatalysts for the transition metals of subgroup VIII, especially rhodium, catalyzed hydroformylation of olefins in particular are suitable, as well as a process for the preparation of aldehydes from α-olefins as well as from internal and / or branched olefins or from higher-boiling ones To provide olefins (with more than 7 carbon atoms).

Obwohl viele phosphorhaltige Liganden für die Rhodium-Niederdruck-Hydroformylierung. bekannt sind (u.a. Arylphosphane, Alkylphosphane, Chelatphosphane, Monophosphite, Chelatphosphite, Phosphole und Phosphabenzole, siehe WO 97/46 507), wurde der Einsatz von η5-Phospholyl- komplexen bisher nicht erwogen. Es wurde nun gefunden, daß diese Liganden als Cokatalysatoren für die Hydroformylierung von Olefinen hochaktiv und damit hervorragend geeignet sind. Bislang waren keine Anwendungen in der Hydroformylierung bekannt.Although many phosphorus ligands for rhodium low pressure hydroformylation. are known (including arylphosphines, alkylphosphines, chelate phosphines, monophosphites, chelate phosphites, phospholes and phosphabenzenes, see WO 97/46 507), the use of η 5 -phospholyl complexes has not previously been considered. It has now been found that these ligands are highly active as cocatalysts for the hydroformylation of olefins and are therefore extremely suitable. No applications in hydroformylation were previously known.

Die Aufgabe wird somit gelöst durch ein Verfahren zur Herstellung von Aldehyden durch Hydroformylierung von Olefinen mit CO/H2 in Gegenwart von Komplexen von Übergangsmetallen der VIII. Nebengruppe des Periodensystems der Elemente bei Temperaturen von 20 bis 200°C und Drücken von Atmosphärendruck bis 700 bar, wobei man Katalysatoren mit zur Komplexbildung befähigten η5-Phospholylkomplexen als Liganden verwendet. Dabei ist das Übergangsmetall (η1-Metall) Rhodium.The object is thus achieved by a process for the preparation of aldehydes by hydroformylation of olefins with CO / H 2 in the presence of complexes of transition metals of subgroup VIII of the periodic table of the elements at temperatures from 20 to 200 ° C. and pressures from atmospheric pressure to 700 bar , where catalysts with η 5 -phospholyl complexes capable of complex formation are used as ligands. The transition metal (η 1 metal) is rhodium.

Die η5-Phospholylkomplexe sind ausgewählt aus den allgemeinen Strukturen I und V

Figure 00030001
Figure 00030002
in denen R1 bis R4 unabhängig voneinander Wasserstoff, C1-12-Alkyl-, C7-12-Aralkyl-, C7-12-Alkaryl- oder C6-12-Arylreste bedeuten oder für die Reste COO-M+, SO3 -M+, NR3 +X-, OR, NR2, COOR, SR, (CHRCH2O)xR, (CH2NR)xR oder (CH2CH2NR)xR stehen, wobei R jeweils gleiche oder verschiedene Reste ausgewählt aus Wasserstoff, C1-12-Alkyl- und C6-12-Arylresten, M+ ein Kation und X- ein Anion und x die Zahlen von 1 bis 120 bedeuten und wobei die Reste R1 bis R4 zu anellierten Ringen verbunden sein können, und in denen MLn für ein Metallkomplexfragment steht und W eine Brücke in Form einer kovalenten Bindung oder einer Kette aus 1 bis 10 Atomen, die Bestandteil einer cyclischen oder aromatischen Verbindung sein kann, oder eine Komplexverbindung ist und wobei die η5-Phospholylkomplexeinheiten in 2-oder 3-Stellung zum Phosphor verknüpft sind, wobei die nicht für die Brücke verwendeten 2- und 3-Positionen durch Reste wie für R1 bis R4 beschrieben substituiert sein können, und wobei einer oder mehrere der Substituenten R1 bis R4 ein über eine weitere Brücke gebundener η5-Phospholylkomplex der Formel I sein kann. Vorzugsweise ist W eine Brücke in Form einer Ferroceneinheit. Bevorzugte Reste R1 bis R4 sind H, Methyl und Phenyl.The η 5 -phospholyl complexes are selected from the general structures I and V.
Figure 00030001
Figure 00030002
in which R 1 to R 4 independently of one another denote hydrogen, C 1-12 alkyl, C 7-12 aralkyl, C 7-12 alkaryl or C 6-12 aryl radicals or for the radicals COO - M + , SO 3 - M + , NR 3 + X - , OR, NR 2 , COOR, SR, (CHRCH 2 O) x R, (CH 2 NR) x R or (CH 2 CH 2 NR) x R, where R in each case the same or different radicals selected from hydrogen, C 1-12 alkyl and C 6-12 aryl radicals, M + is a cation and X - is an anion and x is the number from 1 to 120 and where the radicals R 1 to R 4 can be linked to fused rings, and in which ML n stands for a metal complex fragment and W is a bridge in the form of a covalent bond or a chain of 1 to 10 atoms, which can be part of a cyclic or aromatic compound, or is a complex compound and wherein the η 5 -phospholyl complex units are linked in the 2- or 3-position to the phosphorus, the 2- and 3-positions not used for the bridge being replaced by radicals such as for R 1 to R 4 can be substituted, and one or more of the substituents R 1 to R 4 can be an η 5 -phospholyl complex of the formula I bonded via a further bridge. W is preferably a bridge in the form of a ferrocene unit. Preferred radicals R 1 to R 4 are H, methyl and phenyl.

L ist ausgewählt aus Cyclopentadienyl, CO, Halogen und Phosphan und Gemischen davon.L is selected from cyclopentadienyl, CO, halogen and Phosphine and mixtures thereof.

Als η5-gebundene Metalle werden Zirconium, Wolfram, Mangan, Eisen, Ruthenium, Cobalt verwendet. Mindestens einer der Substituenten R1 bis R4 kann eine zusätzliche, zur Koordination befähigte dreibindige Phosphorgruppierung aufweisen, wodurch ein zwei- oder mehrzähniger Ligand entsteht. Besonders bevorzugt sind Phosphan-, Phosphinit-, Phosphonit- oder Phosphabenzolgruppierungen. Auch eine Stickstoffgruppierung, vorzugsweise Pyridingruppierung, kann vorliegen.Zirconium, tungsten, manganese, iron, ruthenium, cobalt are used as η 5 -bound metals. At least one of the substituents R 1 to R 4 can have an additional, trivalent phosphorus group capable of coordination, which results in a bidentate or multidentate ligand. Phosphane, phosphinite, phosphonite or phosphabenzene groups are particularly preferred. A nitrogen grouping, preferably pyridine grouping, can also be present.

Beispielhaft werden folgende η5-Phospholylkomplexe genannt:

Figure 00040001
Figure 00040002
Figure 00040003
Figure 00050001
Figure 00050002
The following η 5 -phospholyl complexes are mentioned as examples:
Figure 00040001
Figure 00040002
Figure 00040003
Figure 00050001
Figure 00050002

Diese Auflistung dient der Erläuterung der angewandten Begriffe. Cy bedeutet Cyclohexyl, Ph Phenyl.This list is used to explain the terms used. Cy means Cyclohexyl, Ph phenyl.

Die Synthesen von η5-Phospholyl- und η5-Polyphospholylkomplexen sind z.B. in K. B. Dillon, F. Mathey, J. F. Nixon, Phosphorus: The Carbon Copy, J. Wiley, West Sussex, 1998, Chapter 9 (und dort zitierte Literatur) sowie in C. Ganter, C. Glinsböckel, B. Ganter, Eur. J. Inorg. Chem. 1998, 1163, in L. Brassat, B. Ganter, C. Ganter, Chem. Eur. J. 1998, 4, 2148 und in C. Ganter, L. Brassat, B. Ganter, Chem. Ber./Recueil 1997, 130, 1771 beschrieben.The syntheses of η 5 -phospholyl and η 5 -polyphospholyl complexes are described, for example, in KB Dillon, F. Mathey, JF Nixon, Phosphorus: The Carbon Copy, J. Wiley, West Sussex, 1998 , Chapter 9 (and the literature cited therein) and in C. Ganter, C. Glinsböckel, B. Ganter, Eur. J. Inorg. Chem. 1998, 1163, in L. Brassat, B. Ganter, C. Ganter, Chem. Eur. J. 1998, 4, 2148 and in C. Ganter, L. Brassat, B. Ganter, Chem. Ber./Recueil 1997, 130, 1771.

WO 98/50392 ("Process to Prepare Bridged Phosphole-Cyclopentadienyl Compounds") beschreibt die Synthese von Phospholen und Phospholylkomplexen, sowie deren Verwendung als Polymerisationskatalysatoren.WO 98/50392 ("Process to Prepare Bridged Phosphole-Cyclopentadienyl Compounds ") describes the synthesis of phospholes and Phospholyl complexes and their use as polymerization catalysts.

Die bevorzugten wirksamen neuen Katalysatoren sind Komplexe der allgemeinen Formel (VI) M'L'n'(CO)m' mit der Bedeutung

M'
Rhodium
L'
zur Komplexbildung befähigter ein- oder mehrzähniger η5-Phospholyl- komplex-Ligand, wie vorstehend definiert, oder Gemisch davon,
n'
mindestens 1,
m'
mindestens 1.
n' und m' können pro Äquivalent M' beispielsweise die Zahlen 1 bis 3 und die Summe von n'+m' kann 2 bis 6 bedeuten, und es können noch weitere Reste wie Hydrido oder Alkyl- oder Acylreste als Liganden enthalten sein.The preferred effective new catalysts are complexes of the general formula (VI) M'L 'n' (CO) m ' with the meaning
M '
rhodium
L '
monodentate or multidentate η 5 -phospholyl complex ligand as defined above, or a mixture thereof, capable of complex formation,
n '
at least 1,
m '
at least 1.
n 'and m' can be, for example, the numbers 1 to 3 per equivalent of M 'and the sum of n' + m 'can mean 2 to 6, and other radicals such as hydrido or alkyl or acyl radicals can also be present as ligands.

Der Katalysator wird vorzugsweise zur Hydroformylierung von Olefinen eingesetzt. Der aktive Carbonylkomplex wird dabei in der Regel in situ, d.h. im Hydroformylierungsreaktor, aus einem Salz oder einer Verbindung des Metalls M', dem Liganden und Kohlenmonoxid gebildet; er kann aber auch getrennt hergestellt und eingesetzt werden.The catalyst is preferably used for hydroformylation used by olefins. The active carbonyl complex is usually in situ, i.e. in the hydroformylation reactor, from a salt or a compound the metal M ', the ligand and carbon monoxide; but he can also are manufactured and used separately.

Werden die Komplexkatalysatoren in situ erzeugt, setzt man einfache Precursorkomplexe wie Rhodiumdicarbonylacetylacetonat oder Rhodiumacetat in Gegenwart der entsprechenden Liganden den Reaktionsbedingungen aus, oder man versetzt Precursorkomplexe mit aktivierenden Zusätzen wie Brönsted- oder Lewis-Säuren oder Lewis-Basen.If the complex catalysts are generated in situ, simple ones are used Precursor complexes such as rhodium dicarbonyl acetylacetonate or rhodium acetate in Presence of the corresponding ligands from the reaction conditions, or activator additives such as Brönsted or are added to precursor complexes Lewis acids or Lewis bases.

Zur in situ-Bildung des Katalysators im Reaktionsgemisch setzt man den Liganden im molaren Verhältnis (gerechnet als Äquivalent Phosphor) zu Rhodium von vorzugsweise 1:1 bis 1000:1 ein. Bevorzugt wird dabei ein inertes Lösungsmittel verwendet. Besonders bevorzugte Lösungsmittel sind die Aldehyde, die durch Umsetzung des jeweiligen Olefins entstehen, sowie die syntheseeigenen Hochsieder, die durch Folgereaktionen des jeweiligen Aldehyds im Hydroformylierungsverfahren entstehen. Bei durch geeignete Substituenten hydrophilisierten Liganden werden bevorzugt Wasser, Alkohole oder andere Lösungsmittel eingesetzt.For the in situ formation of the catalyst in the reaction mixture, the Ligands in a molar ratio (calculated as equivalent phosphorus) Rhodium of preferably 1: 1 to 1000: 1. An inert one is preferred Solvent used. Particularly preferred solvents are Aldehydes, which are formed by the reaction of the respective olefin, and the High boilers in the synthesis, which are caused by subsequent reactions of the respective aldehyde arise in the hydroformylation process. With suitable substituents Hydrophilized ligands are preferably water, alcohols or others Solvent used.

Die Zusammensetzung des im erfindungsgemäßen Hydroformylierungsverfahren eingesetzten Synthesegases CO/H2 kann in weiten Bereichen variiert werden. Beispielsweise kann Synthesegas mit CO/H2-Molverhältnissen von 5:95 bis 70:30 erfolgreich eingesetzt werden, bevorzugt wird Synthesegas mit CO/H2-Verhältnissen von 40:60 bis 60:40, besonders bevorzugt wird ein CO/H2-Verhältnis von etwa 1:1 angewandt.The composition of the synthesis gas CO / H 2 used in the hydroformylation process according to the invention can be varied within wide limits. For example, synthesis gas with CO / H 2 molar ratios from 5:95 to 70:30 can be used successfully, synthesis gas with CO / H 2 ratios from 40:60 to 60:40 is preferred, and CO / H 2 - is particularly preferred. Ratio of about 1: 1 applied.

Hydroformylierungsreaktionen mit den oben beschriebenen Katalysatoren werden vorzugsweise bei einer Temperatur von 20 bis 200°C, insbesondere bei 50 bis 150°C, durchgeführt. Für jedes Katalysatorsystem kann zweckmäßig eine optimale Temperatur experimentell ermittelt werden. Der Reaktionsdruck kann je nach Cokatalysator und Substrat in einem Bereich von Normaldruck bis 700 bar, vorzugsweise bis 300 bar, liegen, wobei man normalerweise Reaktionen in einem Bereich bis zu etwa 30 bar als Niederdruck- und in einem Bereich bis zu etwa 100 bar als Mitteldruck- und über 100 bar als Hochdruckreaktionen bezeichnet.Hydroformylation reactions with the catalysts described above preferably at a temperature of 20 to 200 ° C, especially at 50 to 150 ° C. For each catalyst system one can be useful optimal temperature can be determined experimentally. The reaction pressure can ever for cocatalyst and substrate in a range from normal pressure to 700 bar, preferably up to 300 bar, which are usually reactions in one Range up to about 30 bar as a low pressure and in a range up to about 100 bar as medium pressure and over 100 bar as high pressure reactions.

Dabei arbeitet man in der Regel mit dem homogen im Reaktionsmedium gelösten Katalysator, der vom Austrag der Hydroformylierungsreaktion abgetrennt und in die Hydroformylierungsstufe zurückgeführt wird.As a rule, one works with that which is homogeneously dissolved in the reaction medium Catalyst, which is separated from the discharge of the hydroformylation reaction and in the hydroformylation stage is recycled.

Man erhält in der Regel nahezu ausschließlich die entsprechenden Aldehyde in ausgezeichneten Ausbeuten. Besonders aktiv sind mit zweizähnigen Bis(η5phospholyl)komplexen der allgemeinen Formel V modifizierte Hydroformylierungskatalysatoren, mit welchen bei niedrigerem Synthesegasdruck die Hydroformylierung von Olefinen durchgeführt werden kann.
Das Katalysatorsystem ist rückführbar. Die Reaktionsausträge nach Rückführung zeigen gemäß 31P-NMR-Spektroskopie im Rahmen der Meßgenauigkeit keine oder nur eine geringe Zersetzung des Cokatalysators an.The corresponding aldehydes are generally obtained almost exclusively in excellent yields. Hydroformylation catalysts modified with bidentate bis (η 5 phospholyl) complexes of the general formula V, with which the hydroformylation of olefins can be carried out at a lower synthesis gas pressure, are particularly active.
The catalyst system is recyclable. According to 31 P-NMR spectroscopy, the reaction outputs after recycling show no or only a slight decomposition of the cocatalyst within the scope of the measurement accuracy.

Als erfindungsgemäß zu hydroformylierende Olefine kommen α-Olefine oder interne Olefine oder interne, verzweigte Olefine in Betracht. Auch funktionelle Gruppen werden toleriert. Beispielhaft werden folgende Olefine genannt: Ethylen, Propen, 1-Buten, 1-Octen, C5-20 α-Olefine, lineare C5-20 interne Olefine, 2-Buten, verzweigte interne Octen-Gemische, verzweigte interne Nonen-Gemische, verzweigte interne Dodecen-Gemische, Cyclohexen, Styrol, 3-Pentennitril, 4-Pentennitril, 3-Pentensäurealkylester, 4-Pentensäurealkylester, Polypropen, Polyisobutylen. Ebenfalls geeignete Substrate sind Di- oder Polyene mit isolierten oder konjugierten Doppelbindungen. Beispiele sind 1,3-Butadien, 1,5-Hexadien, Vinylcyclohexen, Dicylopentadien, 1,5,9-Cyclooctatrien, Butadienhomo- und -copolymere sowie Polyisobuten.Suitable olefins to be hydroformylated according to the invention are α-olefins or internal olefins or internal, branched olefins. Functional groups are also tolerated. The following olefins are mentioned by way of example: ethylene, propene, 1-butene, 1-octene, C 5-20 α-olefins, linear C 5-20 internal olefins, 2-butene, branched internal octene mixtures, branched internal non-mixtures, branched internal dodecene mixtures, cyclohexene, styrene, 3-pentenenitrile, 4-pentenenitrile, 3-pentenoic acid alkyl ester, 4-pentenoic acid alkyl ester, polypropene, polyisobutylene. Also suitable substrates are di- or polyenes with isolated or conjugated double bonds. Examples are 1,3-butadiene, 1,5-hexadiene, vinylcyclohexene, dicylopentadiene, 1,5,9-cyclooctatriene, butadiene homo- and copolymers and polyisobutene.

Die Erfindung wird durch die folgenden Beispiele näher erläutert:The invention is illustrated by the following examples:

BeispieleExamples Allgemeine VersuchsbeschreibungGeneral description of the experiment

Variante A: Rhodiumprecursor, Ligand und Lösungsmittel wurden unter Stickstoff-Inertgas in einem Schlenkrohr gemischt. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 70 ml oder 100 ml fassenden Autoklaven (Material HC) überführt. Es wurden 5 bar CO/H2 (1:1) kalt aufgepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf die gewünschte Temperatur erhitzt. Über eine Schleuse wurde dann das eingesetzte Olefin mit CO/H2-Überdruck in den Autoklaven gepresst. Darauf wurde sofort mittels CO/H2 (1:1) der gewünschte Reaktionsdruck eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit internem Standard und Korrekturfaktor durchgeführt. Variant A: Rhodium precursor, ligand and solvent were mixed in a Schlenk tube under nitrogen inert gas. The solution obtained was transferred to a 70 ml or 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to the desired temperature within 30 min. The olefin used was then pressed into the autoclave with CO / H 2 overpressure via a lock. The desired reaction pressure was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor.

Variante B: Rhodiumprecursor, Ligand und Lösungsmittel wurden unter Stickstoff-Inertgas in einem Schlenkrohr gemischt. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 70 ml oder 100 ml fassenden Autoklaven (Material HC) überfuhrt. Es wurden 5 bar CO/H2 (1:1) kalt aufgepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf 100°C erhitzt. Nach der Katalysatorpräformierung wurde der Autoklav abgekühlt und entspannt. Über eine Schleuse wurde dann das eingesetzte Olefin mit CO/H2-Überdruck in den Autoklaven gepresst. Das Reaktionsgemisch wurde innerhalb von 30 min erneut auf die gewünschte Temperatur erhitzt. Darauf wurde sofort mittels CO/H2 (1:1) der gewünschte Reaktionsdruck eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit internem Standard und Korrekturfaktor durchgeführt. Variant B: Rhodium precursor, ligand and solvent were mixed under nitrogen inert gas in a Schlenk tube. The solution obtained was transferred to a 70 ml or 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. The reaction mixture was heated to 100 ° C. in the course of 30 min with vigorous stirring using a gassing stirrer. After the catalyst had been preformed, the autoclave was cooled and let down. The olefin used was then pressed into the autoclave with CO / H 2 overpressure via a lock. The reaction mixture was reheated to the desired temperature within 30 minutes. The desired reaction pressure was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor.

Beispiel AExample A Niederdruck-Hydroformylierung von 1-OctenLow pressure hydroformylation of 1-octene

Ausgehend von 1,9 mg (0,007 mmol) Rhodiumdicarbonylacetylacetonat, 60,3 mg (0,179 mmol) 2-[2-(3,4-Dimethylphosphaferrocen-2-yl)ethyl]pyridin, 6,1 g (54 mmol) 1-Octen und 6,0 g Texanol® erhielt man bei 90°C, 10 bar CO/H2 und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante A, 100 ml. Autoklav) einen 1-Octen-Umsatz von 84 %. Die Ausbeute an Nonanalen betrug 45 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 74 % und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 100 %.Starting from 1.9 mg (0.007 mmol) rhodium dicarbonylacetylacetonate, 60.3 mg (0.179 mmol) 2- [2- (3,4-dimethylphosphaferrocen-2-yl) ethyl] pyridine, 6.1 g (54 mmol) 1- Octene and 6.0 g Texanol® were obtained at 90 ° C, 10 bar CO / H 2 and 4 h according to the general experimental procedure (variant A, 100 ml. Autoclave) a 1-octene conversion of 84%. The yield of nonanals was 45%, the selectivity to n-nonanal (n component) was 74% and the selectivity to n-nonanal and 2-methyloctanal (α component) was 100%.

Beispiel BExample B Mitteldruck-Hydroformylierung von trans-2-ButenMedium pressure hydroformylation of trans-2-butene

Ausgehend von 1,8 mg (0,007 mmol) Rhodiumdicarbonylacetylaceton, 66,6 mg (0,198 mmol) 2-[2-(3,4-Dimethylphosphaferrocen-2-yl)ethyl]pyridin, 6,6 g (118 mmol) trans-2-Buten und 6,0 g Toluol erhielt man bei 100°C, 20 bar Gesamtdruck (Eigendruck des Olefins und CO/H2) und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante B, 100 ml Autoklav) einen trans-2-Buten-Umsatz von 23 %. Die Ausbeute an Aldehyden betrug 23 % und die Selektivität zu n-Pentanal (n-Anteil) betrug 29 %.Starting from 1.8 mg (0.007 mmol) of rhodium dicarbonylacetylacetone, 66.6 mg (0.198 mmol) of 2- [2- (3,4-dimethylphosphaferrocen-2-yl) ethyl] pyridine, 6.6 g (118 mmol) of trans- 2-butene and 6.0 g of toluene were obtained at 100 ° C, 20 bar total pressure (intrinsic pressure of the olefin and CO / H 2 ) and 4 h according to the general experimental procedure (variant B, 100 ml autoclave) a trans-2-butene -Turnover of 23%. The yield of aldehydes was 23% and the selectivity to n-pentanal (n content) was 29%.

Beispiel 1example 1 Niederdruck-Hydroformylierung von 1-OctenLow pressure hydroformylation of 1-octene

Ausgehend von 1,9 mg (0,007 mmol) Rhodiumdicarbonylacetylacetonat, 36,5 mg (0,153 mmol) 3,4-Dimethylphosphaferrocen, 6,2 g (55 mmol) 1-Octen und 6,0 g Toluol erhielt man bei 90°C, 10 bar CO/H2 und 4h gemäß der allgemeinen Versuchsdurchführung (Variante A, 100 ml Autoklav) einen 1-Octen-Umsatz von 100 %. Die Ausbeute an Nonanalen betrug 18 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 75 % und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 100 %.Starting from 1.9 mg (0.007 mmol) of rhodium dicarbonyl acetylacetonate, 36.5 mg (0.153 mmol) of 3,4-dimethylphosphaferrocene, 6.2 g (55 mmol) of 1-octene and 6.0 g of toluene were obtained at 90 ° C., 10 bar CO / H 2 and 4 h according to the general test procedure (variant A, 100 ml autoclave) a 1-octene conversion of 100%. The yield of nonanals was 18%, the selectivity to n-nonanal (n component) was 75% and the selectivity to n-nonanal and 2-methyloctanal (α component) was 100%.

Beispiel 2Example 2 Mitteldruck-Hydroformylierung von 1-OctenMedium pressure hydroformylation of 1-octene

Ausgehend von 2,3 mg (0,009 mmol) Rhodiumdicarbonylacetylacetonat, 38,5 mg (0,166 mmol) 3,4-Dimethylphosphaferrocen, 6,3 g (56 mmol) 1-Octen und 6,0 g Toluol erhielt man bei 90°C, 40 bar CO/H2 und 4h gemäß der allgemeinen Versuchsdurchführung (Variante A, 100 ml Autoklav) einen 1-Octen-Umsatz von 99 %. Die Ausbeute an Nonanalen betrug 73 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 63 % und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 97 %.Starting from 2.3 mg (0.009 mmol) of rhodium dicarbonyl acetylacetonate, 38.5 mg (0.166 mmol) of 3,4-dimethylphosphaferrocene, 6.3 g (56 mmol) of 1-octene and 6.0 g of toluene were obtained at 90 ° C., 40 bar CO / H 2 and 4 h according to the general test procedure (variant A, 100 ml autoclave) a 1-octene conversion of 99%. The yield of nonanals was 73%, the selectivity to n-nonanal (n component) was 63% and the selectivity to n-nonanal and 2-methyloctanal (α component) was 97%.

Beispiel 3Example 3 Mitteldruck-Hydroformylierung von trans-2-ButenMedium pressure hydroformylation of trans-2-butene

Ausgehend von 4,4 mg (0,017 mmol) Rhodiumdicarbonylacetylacetonat, 96,2 mg (0,415 mmol) 3,4-Dimethylphosphaferrocen, 14,5 g (258 mmol) trans-2-Buten und 15,0 g Toluol erhielt man bei 100°C, 60 bar Gesamtdruck (Eigendruck des Olefins und CO/H2) und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante B, 100 ml Autoklav) einen trans-2-Buten-Umsatz von 73 %. Die Ausbeute an Aldehyden betrug 73 % und die Selektivität zu n-Pentanal (n-Anteil) betrug 17%.Starting from 4.4 mg (0.017 mmol) of rhodium dicarbonyl acetylacetonate, 96.2 mg (0.415 mmol) of 3,4-dimethylphosphaferrocene, 14.5 g (258 mmol) of trans-2-butene and 15.0 g of toluene were obtained at 100 ° C, 60 bar total pressure (intrinsic pressure of the olefin and CO / H 2 ) and 4 h according to the general test procedure (variant B, 100 ml autoclave) a trans-2-butene conversion of 73%. The yield of aldehydes was 73% and the selectivity to n-pentanal (n component) was 17%.

Beispiel 4Example 4 Mitteldruck-Hydroformylierung von Octen-N2Medium pressure hydroformylation of octene-N2

Ausgehend von 4,6 mg (0,018 mmol) Rhodiumdicarbonylacetylacetonat, 94,9 mg (0,409 mmol) 3,4-Dimethylphosphaferrocen, 15,7 g (140 mmol) Octen-N2 (Isooctengemisch, Verzweigungsgrad 1,06) und 15,0 g Texanol® erhielt man bei 100°C, 60 bar Gesamtdruck gemäß der allgemeinen Versuchsdurchführung (Variante A, 100 ml Autoklav) einen Octen-N2-Umsatz von 32 % nach 4 h Reaktionszeit und 55 % nach 24 h Reaktionszeit. Die Ausbeute an Nonanalen betrug 32 % nach 4 h Reaktionszeit und 55 % nach 24 h Reaktionszeit.Starting from 4.6 mg (0.018 mmol) of rhodium dicarbonylacetylacetonate, 94.9 mg (0.409 mmol) 3,4-dimethylphosphaferrocene, 15.7 g (140 mmol) octene-N2 (Isoocten mixture, degree of branching 1.06) and 15.0 g of Texanol® were obtained from 100 ° C, 60 bar total pressure according to the general test procedure (Variant A, 100 ml autoclave) an octene-N2 conversion of 32% after 4 h Response time and 55% after 24 h reaction time. The yield of nonanal was 32% after 4 h reaction time and 55% after 24 h reaction time.

Beispiel 5Example 5 Mitteldruck-Hydroformylierung von 1-OctenMedium pressure hydroformylation of 1-octene

Ausgehend von 2,0 mg (0,008 mmol) Rhodiumdicarbonylacetylacetonat, 53,0 mg (0,164 mmol) 2-[(3,4-Dimethylphosphaferrocen-2-yl)methyl]pyridin, 6,8 mg (61 mmol) 1-Octen und 6,0 g Texanol® erhielt man bei 90°C, 40 bar CO/H2 und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante A, 100 ml Autoklav) einen 1-Octen-Umsatz von 99 %. Die Ausbeute an Nonanalen betrug 82 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 65 %, und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 97 %.Starting from 2.0 mg (0.008 mmol) of rhodium dicarbonylacetylacetonate, 53.0 mg (0.164 mmol) of 2 - [(3,4-dimethylphosphaferrocen-2-yl) methyl] pyridine, 6.8 mg (61 mmol) of 1-octene and 6.0 g of Texanol® were obtained at 90 ° C, 40 bar CO / H 2 and 4 h according to the general test procedure (variant A, 100 ml autoclave) a 1-octene conversion of 99%. The yield of nonanals was 82%, the selectivity to n-nonanal (n component) was 65%, and the selectivity to n-nonanal and 2-methyloctanal (α component) was 97%.

Beispiel 6Example 6 Mitteldruck-Hydroformylierung von 1-Octen (Rückführung)Medium pressure hydroformylation of 1-octene (recycle)

Die Aldehyde im Reaktionsgemisch von Beispiel 5 wurden bei 100°C unter Vakuum abdestilliert. Zurück blieb eine homogene Lösung, bestehend aus Aktivkatalysator, Texanol® und reaktionseigenen Hochsiedern. Hierzu wurden unter Luftausschluß 6,8 g (61 mmol) 1-Octen gegeben. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 100 ml Autoklav (Material HC) überführt. Es wurden 5 bar CO/H2 (1:1) kalt aufgepresst. Unter käftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf 90°C erhitzt. Daraufhin wurde sofort mittels CO/H2 (1:1) ein Reaktionsdruck von 40 bar CO/H2 eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit von 4 h wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit internem Standard und Korrekturfaktor durchgeführt. Der 1-Octen-Umsatz betrug 67 %, die Ausbeute an Nonanalen betrug 57 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 73 %, und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 100 %. Ein 31P-NMR-Spektrum des Reaktionsaustrages zeigt im Rahmen der Meßgenauigkeit das unveränderte Vorliegen des Cokatalysators. The aldehydes in the reaction mixture of Example 5 were distilled off at 100 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the reaction's own high boilers. For this purpose, 6.8 g (61 mmol) of 1-octene were added in the absence of air. The solution obtained was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring with a gassing stirrer, the reaction mixture was heated to 90 ° C. within 30 minutes. A reaction pressure of 40 bar CO / H 2 was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time of 4 h, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor. The 1-octene conversion was 67%, the yield of nonanals was 57%, the selectivity to n-nonanal (n component) was 73%, and the selectivity to n-nonanal and 2-methyloctanal (α component) 100%. A 31 P-NMR spectrum of the reaction discharge shows the unchanged presence of the cocatalyst within the scope of the measurement accuracy.

Beispiel 7Example 7 Niederdruck-Hydroformylierung von 1-OctenLow pressure hydroformylation of 1-octene

Ausgehend von 2,1 mg (0,008 mmol) Rhodiumdicarbonylacetylacetonat, 57,8 mg (0,171 mmol) 2-[2-(3,4-Dimethylphosphaferrocen-2-yl)ethyl]pyridin, 6,3 mg (56 mmol) 1-Octen und 6,0 g Texanol® erhielt man bei 90°C, 20 bar CO/H2 und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante A, 70 ml Autoklav) einen 1-Octen-Umsatz von 99 %. Die Ausbeute an Nonanalen betrug 76 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 67 %, und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 97 %.Starting from 2.1 mg (0.008 mmol) rhodium dicarbonyl acetylacetonate, 57.8 mg (0.171 mmol) 2- [2- (3,4-dimethylphosphaferrocen-2-yl) ethyl] pyridine, 6.3 mg (56 mmol) 1- Octene and 6.0 g Texanol® were obtained at 90 ° C, 20 bar CO / H 2 and 4 h according to the general experimental procedure (variant A, 70 ml autoclave) a 1-octene conversion of 99%. The yield of nonanals was 76%, the selectivity to n-nonanal (n component) was 67%, and the selectivity to n-nonanal and 2-methyloctanal (α component) was 97%.

Beispiel 8Example 8 Mitteldruck-Hydroformylierung von IsobutenMedium pressure hydroformylation of isobutene

Ausgehend von 3,4 mg (0,011 mmol) Rhodiumdicarbonylacetylacetonat, 104,0 mg (0,322 mmol) 2-[2-(3,4-Dimethylphosphaferrocen-2-yl)ethyl]pyridin, 12,3 g (219 mmol) Isobuten und 10,0 g Texanol® erhielt man bei 100°C, 40 bar Gesamtdruck (Eigendruck des Olefins und CO/H2) und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante B, 70 ml Autoklav) einen Isobuten-Umsatz von 39 %. Die Ausbeute an Aldehyden betrug 39 %, und die Selektivität zu Isovaleraldehyd betrug 100 %.Starting from 3.4 mg (0.011 mmol) of rhodium dicarbonyl acetylacetonate, 104.0 mg (0.322 mmol) of 2- [2- (3,4-dimethylphosphaferrocen-2-yl) ethyl] pyridine, 12.3 g (219 mmol) of isobutene and 10.0 g of Texanol® were obtained at 100 ° C., 40 bar total pressure (intrinsic pressure of the olefin and CO / H 2 ) and 4 h according to the general test procedure (variant B, 70 ml autoclave) an isobutene conversion of 39%. The yield of aldehydes was 39% and the selectivity to isovaleraldehyde was 100%.

Beispiel 9Example 9 Niederdruck-Hydroformylierung von 1-OctenLow pressure hydroformylation of 1-octene

Ausgehend von 1,9 mg (0,007 mmol) Rhodiumdicarbonylacetylacetonat, 61,5 mg (0,164 mmol) 2,5-Diphenylphosphacymantren, 7,3 mg (65 mmol) 1-Octen und 6,0 g Texanol® erhielt man bei 90°C, 10 bar CO/H2 und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante A, jedoch Präformierung bei 90°C und 2 bar CO/H2, 70 ml Autoklav) einen 1-Octen-Umsatz von 99 %. Die Ausbeute an Nonanalen betrug 15 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 47 %, und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 85 %.Starting from 1.9 mg (0.007 mmol) of rhodium dicarbonyl acetylacetonate, 61.5 mg (0.164 mmol) of 2,5-diphenylphosphacymantrene, 7.3 mg (65 mmol) of 1-octene and 6.0 g of Texanol® were obtained at 90 ° C. , 10 bar CO / H 2 and 4 h according to the general test procedure (variant A, but preforming at 90 ° C and 2 bar CO / H 2 , 70 ml autoclave) a 1-octene conversion of 99%. The yield of nonanals was 15%, the selectivity to n-nonanal (n component) was 47%, and the selectivity to n-nonanal and 2-methyloctanal (α component) was 85%.

Beispiel 10Example 10 Niederdruck-Hydroformylierung von 1-Octen (Rückführung)Low pressure hydroformylation of 1-octene (recycle)

Die Aldehyde im Reaktionsgemisch von Beispiel 9 wurden bei 100°C unter Vakuum abdestilliert. Zurück blieb eine homogene Lösung bestehend aus Aktivkatalysator, Texanol® und reaktionseigenen Hochsiedern. Hierzu wurden unter Luftausschluß 6,7 g (60 mmol) 1-Octen gegeben. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 70 ml Autoklav (Material HC) überführt. Es wurden 2 bar CO/H2 (1:1) kalt aufgepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf 90°C erhitzt. Daraufhin wurde sofort mittels CO/H2 (1:1) der gewünschte Reaktionsdruck eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit von 4 h wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit internem Standard und Korrekturfaktor durchgeführt. Der 1-Octen-Umsatz betrug 99 %, die Ausbeute an Nonanalen betrug 32 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 55 %, und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 90 %.The aldehydes in the reaction mixture of Example 9 were distilled off at 100 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the company's own high boilers. To this end, 6.7 g (60 mmol) of 1-octene were added in the absence of air. The solution obtained was transferred to a 70 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 2 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to 90 ° C. within 30 minutes. The desired reaction pressure was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time of 4 h, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor. The 1-octene conversion was 99%, the yield of nonanals was 32%, the selectivity to n-nonanal (n component) was 55%, and the selectivity to n-nonanal and 2-methyloctanal (α component) 90%.

Beispiel 11Example 11 Mitteldruck-Hydroformylierung von 1-OctenMedium pressure hydroformylation of 1-octene

Ausgehend von 2,1 mg (0,008 mmol) Rhodiumdicarbonylacetylacetonat, 70,7 mg (0,189 mmol) 2,5-Diphenylphosphacymantren, 6,0 g (23 mmol) 1-Octen und 6,0 g Texanol® erhielt man bei 90°C, 40 bar CO/H2 und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante A, 70 ml Autoklav) einen 1-Octen-Umsatz von 100 %. Die Ausbeute an Nonanalen betrug 83 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 40 %, und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 77 %.Starting from 2.1 mg (0.008 mmol) of rhodium dicarbonyl acetylacetonate, 70.7 mg (0.189 mmol) of 2,5-diphenylphosphacymantrene, 6.0 g (23 mmol) of 1-octene and 6.0 g of Texanol® were obtained at 90 ° C , 40 bar CO / H 2 and 4 h according to the general test procedure (variant A, 70 ml autoclave) a 1-octene conversion of 100%. The yield of nonanals was 83%, the selectivity to n-nonanal (n component) was 40%, and the selectivity to n-nonanal and 2-methyloctanal (α component) was 77%.

Beispiel 12Example 12 Mitteldruck-Hydroformylierung von 1-Octen (Rückführung)Medium pressure hydroformylation of 1-octene (recycle)

Die Aldehyde im Reaktionsgemisch von Beispiel 11 wurden bei 100°C unter Vakuum abdestilliert. Zurück blieb eine homogene Lösung, bestehend aus Aktivkatalysator, Texanol® und reaktionseigenen Hochsiedern. Hierzu wurden unter Luftausschluß 6,0 g (23 mmol) 1-Octen gegeben. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 70 ml Autoklav (Material HC) überführt. Es wurden 5 bar CO/H2 (1:1) kalt aufgepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf 90°C erhitzt. Daraufhin wurde sofort mittels CO/H2 (1:1) ein Reaktionsdruck von 40 bar CO/H2 eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit von 4 h wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit internem Standard und Korrekturfaktor durchgeführt. Der 1-Octen-Umsatz betrug 100 %, die Ausbeute an Nonanalen betrug 92 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 26 % und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 65 %. Ein 31P-NMR-Spektrum des Reaktionaustrages zeigte im Rahmen der Meßgenauigkeit das unveränderte Vorliegen des Cokatalysators.The aldehydes in the reaction mixture of Example 11 were distilled off at 100 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the reaction's own high boilers. 6.0 g (23 mmol) of 1-octene were added to this in the absence of air. The solution obtained was transferred to a 70 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to 90 ° C. within 30 minutes. A reaction pressure of 40 bar CO / H 2 was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time of 4 h, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor. The 1-octene conversion was 100%, the yield of nonanals was 92%, the selectivity to n-nonanal (n component) was 26% and the selectivity to n-nonanal and 2-methyloctanal (α component) was 65 %. A 31 P-NMR spectrum of the reaction output showed the unchanged presence of the cocatalyst within the scope of the measurement accuracy.

Beispiel 13Example 13 Mitteldruck-Hydroformylierung von trans-2-ButenMedium pressure hydroformylation of trans-2-butene

Ausgehend von 2,1 mg (0,008 mmol) Rhodiumdicarbonylacetylacetonat, 66,3 mg (0,177 mmol) 2,5-Diphenylphosphacymantren, 3,5 g (62 mmol) trans-2-Buten und 6,0 g Texanol® erhielt man bei 100°C, 40 bar Gesamtdruck (Eigendruck des Olefins und CO/H2) und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante B, 70 ml Autoklav) einen trans-2-Buten-Umsatz von 66 %. Die Ausbeute an Aldehyden betrug 66 %, und die Selektivität zu n-Pentanal (n-Anteil) betrug 37 %.Starting from 2.1 mg (0.008 mmol) of rhodium dicarbonyl acetylacetonate, 66.3 mg (0.177 mmol) of 2,5-diphenylphosphacymantrene, 3.5 g (62 mmol) of trans-2-butene and 6.0 g of Texanol® were obtained at 100 ° C, 40 bar total pressure (intrinsic pressure of the olefin and CO / H 2 ) and 4 h according to the general test procedure (variant B, 70 ml autoclave) a trans-2-butene conversion of 66%. The yield of aldehydes was 66% and the selectivity to n-pentanal (n component) was 37%.

Beispiel 14Example 14 Mitteldruck-Hydroformylierung von trans-2-Buten (Rückführung)Medium pressure hydroformylation of trans-2-butene (recycling)

Die Aldehyde im Reaktionsgemisch von Beispiel 13 wurden bei 70°C unter Vakuum abdestilliert. Zurück blieb eine homogene Lösung, bestehend aus Aktivkatalysator, Texanol® und reaktionseigenen Hochsiedern. Die Lösung wurde in einen mit CO/H2 (1:1) gespülten 70 ml Autoklav (Material HC) überführt. Über eine Schleuse wurden dann 4,5 g (80 mmol) trans-2-Buten mit CO/H2-Überdruck in den Autoklaven gepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf 100°C erhitzt. Daraufhin wurde sofort mittels CO/H2 (1:1) ein Reaktionsdruck von 40 bar (Eigendruck des Olefins und CO/H2) eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit von 4 h wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit internem Standard und Korrekturfaktor durchgeführt. Der trans-2-Buten-Umsatz betrug 65 %, die Ausbeute an Nonanalen betrug 65 %, und die Selektivität zu n-Pentanal (n-Anteil) betrug 35 %. Ein 31P-NMR-Spektrum des Reaktionsaustrages zeigte im Rahmen der Meßgenauigkeit das nahezu unveränderte Vorliegen des Cokatalysators.The aldehydes in the reaction mixture of Example 13 were distilled off at 70 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the reaction's own high boilers. The solution was transferred to a 70 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 4.5 g (80 mmol) of trans-2-butene with CO / H 2 overpressure were then pressed into the autoclave via a lock. The reaction mixture was heated to 100 ° C. in the course of 30 min with vigorous stirring using a gassing stirrer. A reaction pressure of 40 bar (intrinsic pressure of the olefin and CO / H 2 ) was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time of 4 h, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor. The trans-2-butene conversion was 65%, the yield of nonanals was 65%, and the selectivity to n-pentanal (n component) was 35%. A 31 P-NMR spectrum of the reaction discharge showed the almost unchanged presence of the cocatalyst within the scope of the measurement accuracy.

Vergleichsbeispiel 1Comparative Example 1 Mitteldruck-Hydroformylierung von trans-2-ButenMedium pressure hydroformylation of trans-2-butene

Ausgehend von 4,9 mg (0,019 mmol) Rhodiumdicarbonylacetylacetonat, 113,1 mg (0,431 mmol) Triphenylphosphan, 12,9 g (230 mmol) trans-2-Buten und 15,3 g Toluol erhielt man bei 100°C, 40 bar Gesamtdruck (Eigendruck des Olefins und CO/H2) und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante B, 100 ml Autoklav) einen trans-2-Buten-Umsatz von 47 %. Die Ausbeute an Aldehyden betrug 47 %, und die Selektivität zu n-Pentanal (n-Anteil) betrug 3 %.Starting from 4.9 mg (0.019 mmol) of rhodium dicarbonylacetylacetonate, 113.1 mg (0.431 mmol) of triphenylphosphine, 12.9 g (230 mmol) of trans-2-butene and 15.3 g of toluene were obtained at 100 ° C., 40 bar Total pressure (intrinsic pressure of the olefin and CO / H 2 ) and 4 h according to the general test procedure (variant B, 100 ml autoclave) a trans-2-butene conversion of 47%. The yield of aldehydes was 47% and the selectivity to n-pentanal (n component) was 3%.

Beispiel 15Example 15 Mitteldruck-Hydroformylierung von Octen-N2Medium pressure hydroformylation of octene-N2

Ausgehend von 3,4 mg (0,013 mmol) Rhodiumdicarbonylacetylacetonat, 102,8 mg (0,275 mmol) 2,5-Diphenylphosphacymantren, 10,7 g (95 mmol), Octen-N2 (Isooctengemisch, Verzweigungsgrad 1,06) und 10,0 g Texanol® erhielt man bei 100°C, 60 bar Gesamtdruck gemäß der allgemeinen Versuchsdurchführung (Variante A, 100 ml Autoklav) einen Octen-N2-Umsatz von 74 % nach 24 h Reaktionszeit. Die Ausbeute an Nonanalen betrug 74 % nach 24 h Reaktionszeit.Starting from 3.4 mg (0.013 mmol) rhodium dicarbonylacetylacetonate, 102.8 mg (0.275 mmol) 2,5-diphenylphosphacymantrene, 10.7 g (95 mmol), octene-N2 (Isoocten mixture, degree of branching 1.06) and 10.0 g Texanol® were obtained from 100 ° C, 60 bar total pressure according to the general test procedure (Variant A, 100 ml autoclave) an octene-N2 conversion of 74% after 24 h Reaction time. The yield of nonanals was 74% after a reaction time of 24 h.

Beispiel 16Example 16 Mitteldruck-Hydroformylierung von Octen-N2 (Rückführung)Medium pressure hydroformylation of octene-N2 (recycle)

Die Aldehyde im Reaktionsgemisch von Beispiel 15 wurden bei 100°C unter Vakuum abdestilliert. Zurück blieb eine homogene Lösung, bestehend aus Aktivkatalysator, Texanol® und reaktionseigenen Hochsiedern. Die Lösung wurde in einen mit CO/H2 (1:1) gespülten 100 ml Autoklav (Material HC) überführt. Hierzu wurden unter Luftausschluß 10,0 g (89 mmol) Octen-N2 gegeben. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 100 ml Autoklav (Material HC) überführt. Es wurden 5 bar CO/H2 (1:1) kalt aufgepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf 90°C erhitzt. Daraufhin wurde sofort mittels CO/H2 (1:1) ein Reaktionsdruck von 60 bar CO/H2 eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit internem Standard und Korrekturfaktor durchgeführt. Der Octen-N2-Umsatz betrug 60 % nach 4 h Reaktionszeit und 88 % nach 24 h Reaktionszeit. Die Ausbeute an Nonanalen betrug 60 % nach 4 h Reaktionszeit und 88 % nach 24 h Reaktionszeit. Ein 31P-NMR-Spektrum des Reaktionsaustrages zeigte im Rahmen der Meßgenauigkeit das nahezu unveränderte Vorliegen des Cokatalysators.The aldehydes in the reaction mixture of Example 15 were distilled off at 100 ° C. under vacuum. What remained was a homogeneous solution consisting of an active catalyst, Texanol® and the reaction's own high boilers. The solution was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). For this purpose, 10.0 g (89 mmol) of octene-N2 were added in the absence of air. The solution obtained was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 5 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to 90 ° C. within 30 minutes. A reaction pressure of 60 bar CO / H 2 was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by GC with an internal standard and correction factor. The octene-N2 conversion was 60% after 4 h reaction time and 88% after 24 h reaction time. The yield of nonanals was 60% after 4 h reaction time and 88% after 24 h reaction time. A 31 P-NMR spectrum of the reaction discharge showed the almost unchanged presence of the cocatalyst within the scope of the measurement accuracy.

Vergleichsbeispiel 2Comparative Example 2 Mitteldruck-Hydroformylierung von Octen-N2Medium pressure hydroformylation of octene-N2

Ausgehend von 4,4 mg (0,017 mmol) Rhodiumdicarbonylacetylacetonat, 107,3 mg (0,409 mmol) Triphenylphosphan, 16,2 g (144 mmol) Octen-N2 (Isooctengemisch, Verzweigungsgrad 1,06) und 15,3 g Texanol® erhielt man bei 100°C, 60 bar Gesamtdruck gemäß der allgemeinen Versuchsdurchführung (Variante A, 100 ml Autklav) einen Octen-N2-Umsatz von 39 % nach 24 h Reaktionszeit. Die Ausbeute an Nonanalen betrug 39 % nach 24 h Reaktionszeit.Starting from 4.4 mg (0.017 mmol) rhodium dicarbonylacetylacetonate, 107.3 mg (0.409 mmol) triphenylphosphine, 16.2 g (144 mmol) octene-N2 (Isoocten mixture, degree of branching 1.06) and 15.3 g of Texanol® were obtained from 100 ° C, 60 bar total pressure according to the general test procedure (Variant A, 100 ml autoclave) an octene-N2 conversion of 39% after 24 h Reaction time. The yield of nonanals was 39% after a reaction time of 24 h.

Beispiel 17Example 17 Niederdruck-Hydroformylierung von 1-OctenLow pressure hydroformylation of 1-octene

0,7 mg (0,003 mmol) Rhodiumdicarbonylacetylacetonat, 17,8 mg (0,026 mmol) 1,1'-Bis[(3,4-dimethylphosphaferrocen-2-yl)methyl]ferrocen und 2,3 ml Toluol wurden unter Stickstoff-Inertgas in einem Schlenkrohr gemischt. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 50 ml Glasautoklaven überführt. Es wurden 10 bar CO/H2 (1:1) kalt aufgepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf eine Temperatur von 100°C erhitzt. Danach wurde auf eine Temperatur von 80°C temperiert, und anschließend wurde der Autoklav entspannt. Mittels einer Spritze wurden 2,2 g (20 mmol) 1-Octen im CO/H2-Gegenstrom zugegeben. Daraufhin wurde sofort mittels CO/H2, (1:1) ein Reaktionsdruck von 10 bar eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit Korrekturfaktoren durchgeführt. Der 1-Octen-Umsatz betrug 92 %, die Ausbeute an Nonanalen betrug 83 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 69 % und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 100 %.0.7 mg (0.003 mmol) of rhodium dicarbonylacetylacetonate, 17.8 mg (0.026 mmol) of 1,1'-bis [(3,4-dimethylphosphaferrocen-2-yl) methyl] ferrocene and 2.3 ml of toluene were added under nitrogen inert gas mixed in a Schlenk tube. The solution obtained was transferred to a 50 ml glass autoclave flushed with CO / H 2 (1: 1). 10 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to a temperature of 100 ° C. within 30 minutes. The temperature was then raised to 80 ° C. and the autoclave was then depressurized. 2.2 g (20 mmol) of 1-octene were added in a CO / H 2 countercurrent using a syringe. A reaction pressure of 10 bar was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by means of GC with correction factors. The 1-octene conversion was 92%, the yield of nonanals was 83%, the selectivity to n-nonanal (n component) was 69% and the selectivity to n-nonanal and 2-methyloctanal (α component) was 100 %.

Beispiel 18Example 18 Niederdruck-Hydroformylierung von 1-OctenLow pressure hydroformylation of 1-octene

0,7 mg (0,003 mmol) Rhodiumdicarbonylacetylacetonat, 8,8 mg (0,013 mmol) 1,1'-Bis[(3,4-dimethylphosphaferrocen-2-yl)methyl]ferrocen und 2,3 ml Toluol wurden unter Stickstoff-Inertgas in einem Schlenkrohr gemischt. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 50 ml Glasautoklaven überführt. Es wurden 10 bar CO/H2 (1:1) kalt aufgepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf eine Temperatur von 100°C erhitzt. Danach wurde auf eine Temperatur von 80°C temperiert, und anschließend wurde der Autoklav entspannt. Mittels einer Spritze wurden 2,2 g (20 mmol) 1-Octen im CO/H2-Gegenstrom zugegeben. Daraufhin wurde sofort mittels CO/H2 (1:1) ein Reaktionsdruck von 10 bar eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit Korrekturfaktoren durchgeführt. Der 1-Octen-Umsatz betrug 71 %, die Ausbeute an Nonanalen betrug 60 %, die Selektivität zu n-Nonanal (n-Anteil) betrug 70 %, und die Selektivität zu n-Nonanal und 2-Methyloctanal (α-Anteil) betrug 100 %.0.7 mg (0.003 mmol) of rhodium dicarbonyl acetylacetonate, 8.8 mg (0.013 mmol) of 1,1'-bis [(3,4-dimethylphosphaferrocen-2-yl) methyl] ferrocene and 2.3 ml of toluene were added under nitrogen inert gas mixed in a Schlenk tube. The solution obtained was transferred to a 50 ml glass autoclave flushed with CO / H 2 (1: 1). 10 bar CO / H 2 (1: 1) were pressed in cold. With vigorous stirring using a gassing stirrer, the reaction mixture was heated to a temperature of 100 ° C. within 30 minutes. The temperature was then raised to 80 ° C. and the autoclave was then depressurized. 2.2 g (20 mmol) of 1-octene were added in a CO / H 2 countercurrent using a syringe. A reaction pressure of 10 bar was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by means of GC with correction factors. The 1-octene conversion was 71%, the yield of nonanals was 60%, the selectivity to n-nonanal (n component) was 70%, and the selectivity to n-nonanal and 2-methyloctanal (α component) 100%.

Beispiel 19Example 19 Mitteldruck-Hydroformylierung von trans-2-ButenMedium pressure hydroformylation of trans-2-butene

Ausgehend von 4,2 mg (0,016 mmol) Rhodiumdicarbonylacetylacetonat, 110,0 mg (0,163 mmol) 1,1'-Bis[(3,4-dimethylphosphaferrocen-2-yl)methyl]ferrocen, 14,7 g (262 mmol) trans-2-Buten und 15,0 g Toluol erhielt man bei 100°C, 40 bar Gesamtdruck (Eigendruck des Olefins und CO/H2) und 4 h gemäß der allgemeinen Versuchsdurchführung (Variante B, jedoch Präformierung bei 80°C und 20 bar, 100 ml Autoklav) einen trans-2-Buten-Umsatz von 72 %. Die Ausbeute an Aldehyden betrug 72 % und die Selektivität zu n-Pentanal (n-Anteil) betrug 13 %.Starting from 4.2 mg (0.016 mmol) rhodium dicarbonyl acetylacetonate, 110.0 mg (0.163 mmol) 1,1'-bis [(3,4-dimethylphosphaferrocen-2-yl) methyl] ferrocene, 14.7 g (262 mmol) Trans-2-butene and 15.0 g of toluene were obtained at 100 ° C, 40 bar total pressure (intrinsic pressure of the olefin and CO / H 2 ) and 4 h according to the general test procedure (variant B, but preforming at 80 ° C and 20 bar, 100 ml autoclave) a trans-2-butene conversion of 72%. The yield of aldehydes was 72% and the selectivity to n-pentanal (n component) was 13%.

Beispiel 20Example 20 Mitteldruck-Hydroformylierung von trans-2-Buten (Rückführung)Medium pressure hydroformylation of trans-2-butene (recycling)

Die Aldehyde im Reaktionsgemisch von Beispiel 19 wurden bei 70°C unter Vakuum abdestilliert. Zurück blieb eine homogene Lösung, bestehend aus Aktivkatalysator, Toluol und reaktionseigenen Hochsiedern, welche mit Toluol auf eine Gesamtmenge von 15 g ergänzt wurde. Die erhaltene Lösung wurde in einen mit CO/H2 (1:1) gespülten 100 ml Autoklav (Material HC) überfuhrt. Es wurden 20 bar CO/H2 (1:1) kalt aufgepresst. Unter kräftigem Rühren mit einem Begasungsrührer wurde das Reaktionsgemisch innerhalb von 30 min auf 80°C erhitzt. Nach der Katalysatorpräformierung wurde der Autoklav abgekühlt und entspannt. Über eine Schleuse wurden dann 15,7 g (280 mmol) trans-2-Buten und CO/H2-Überdruck in den Autoklaven gepresst. Das Reaktionsgemisch wurde innerhalb von 30 min erneut auf eine Temperatur von 100°C erhitzt. Daraufhin wurde sofort mittels CO/H2 (1:1) ein Reaktionsdruck von 40 bar (Eigendruck des Olefins und CO/H2) eingestellt. Während der Reaktion wurde der Druck im Reaktor durch Nachpressen über einen Druckregler auf Druckniveau gehalten. Nach der Reaktionszeit wurde der Autoklav abgekühlt, entspannt und entleert. Eine Analyse des Reaktionsgemisches wurde mittels GC mit Korrekturfaktoren durchgeführt. Der trans-2-Buten-Umsatz betrug 54 %, die Ausbeute an Pentanalen betrug 54 % und die Selektivität zu n-Pentanal (n-Anteil) betrug 21 %.The aldehydes in the reaction mixture of Example 19 were distilled off at 70 ° C under vacuum. What remained was a homogeneous solution consisting of an active catalyst, toluene and high-boilers from the reaction, which was supplemented with toluene to a total amount of 15 g. The solution obtained was transferred to a 100 ml autoclave (material HC) rinsed with CO / H 2 (1: 1). 20 bar CO / H 2 (1: 1) were pressed in cold. The reaction mixture was heated to 80 ° C. in the course of 30 minutes with vigorous stirring using a gassing stirrer. After the catalyst had been preformed, the autoclave was cooled and let down. 15.7 g (280 mmol) of trans-2-butene and CO / H 2 overpressure were then pressed into the autoclave via a lock. The reaction mixture was reheated to a temperature of 100 ° C. within 30 minutes. A reaction pressure of 40 bar (intrinsic pressure of the olefin and CO / H 2 ) was then immediately set using CO / H 2 (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. The reaction mixture was analyzed by means of GC with correction factors. The trans-2-butene conversion was 54%, the yield of pentanals was 54% and the selectivity to n-pentanal (n component) was 21%.

Beispiel 21Example 21 Hydroformylierung von 3-Pentennitril mit 1,1'-Bis[(3,4-dimethylphosphaferrocen-2-yl)methyl]ferrocenHydroformylation of 3-pentenenitrile with 1,1'-bis [(3,4-dimethylphosphaferrocen-2-yl) methyl] ferrocene

0,7 mg (0,003 mmol) Rh(CO)2acac wurden mit 3 g Xylol und 17,8 mg (0,026 mmol) Ligand vorgelegt und bei 100°C und 15 bar Synthesegas 30 min lang präformiert. Anschließend wurden 1,5 g (18,5 mmol) 3-Pentennitril zugespritzt und der Druck auf 15 bar eingestellt. Nach einer Reaktionszeit von 4 h wurde bei einem Umsatz von 71 % eine Aldehydausbeute von 69 % erzielt. Die Linearität betrug 2 %, der α-Anteil 26 %.0.7 mg (0.003 mmol) Rh (CO) 2 acac were initially charged with 3 g xylene and 17.8 mg (0.026 mmol) ligand and preformed for 30 min at 100 ° C. and 15 bar synthesis gas. 1.5 g (18.5 mmol) of 3-pentenenitrile were then injected and the pressure was adjusted to 15 bar. After a reaction time of 4 h, an aldehyde yield of 69% was achieved with a conversion of 71%. The linearity was 2%, the α portion was 26%.

Beispiel 22Example 22 Hydroformylierung von 4-Pentennitril mit 1,1'-Bis[(3,4-dimethylphosphaferrocen-2-yl)methyl]ferrocenHydroformylation of 4-pentenenitrile with 1,1'-bis [(3,4-dimethylphosphaferrocen-2-yl) methyl] ferrocene

0,7 mg (0,003 mmol) Rh(CO)2acac wurden mit 3 g Xylol und 17,8 mg (0,026 mmol) Ligand vorgelegt und bei 100°C und 15 bar Synthesegas 30 min lang präformiert. Anschließend wurden 1,5 g (18,5 mmol) 4-Pentennitril zugespritzt und der Druck auf 15 bar eingestellt. Nach einer Reaktionszeit von 4 h wurde bei einem Umsatz von 42 % eine Aldehydausbeute von 42 % erzielt. Die Linearität betrug 52 %, der α-Anteil 100 %.0.7 mg (0.003 mmol) Rh (CO) 2 acac were initially charged with 3 g xylene and 17.8 mg (0.026 mmol) ligand and preformed for 30 min at 100 ° C. and 15 bar synthesis gas. 1.5 g (18.5 mmol) of 4-pentenenitrile were then injected and the pressure was adjusted to 15 bar. After a reaction time of 4 h, an aldehyde yield of 42% was achieved with a conversion of 42%. The linearity was 52%, the α portion 100%.

Claims (4)

  1. A process for preparing aldehydes by hydroformylation of olefins using CO/H2 in the presence of complexes of transition metals of transition group VIII of the Periodic Table of the Elements at from 20 to 200°C and pressures from atmospheric pressure to 700 bar, wherein catalysts having η5-phospholyl complexes capable of complex formation as ligands are used, the transition metal used as η1-metal is rhodium and the η5-phospholyl complexes are selected from among the structures I and V
    Figure 00240001
    Figure 00240002
    in which R1 to R4 are, independently of one another, hydrogen, C1-12-alkyl, C7-12-aralkyl, C7-12-alkaryl or C6-12-aryl radicals, where at least one of the substituents R1 to R4 can have an additional nitrogen group or an additional trivalent phosphorus group capable of coordination, resulting in a bidentate or polydentate ligand, or the radicals COC-M+, SO3 -M+, NR3 +X-, OR, NR2, COOR, SR, (CHRCH2O)xR, (CH2NR)xR or (CH2CH2NR)xR, where R are in each case identical or different radicals selected from among hydrogen, C1-12-alkyl and C6-12-aryl radicals, M+ is a cation and X- is an anion and x is from 1 to 120, where the radicals R1 to R4 may be joined to form fused rings, and in which MLn is a metal complex fragment and W is a bridge in the form of a covalent bond or a chain of from 1 to 10 atoms which may be part of a cyclic or aromatic compound, or is a complex, and where the η5-phospholyl complex units are linked in the 2 or 3 position relative to the phosphorus, where the 2 and 3 positions not used for the bridge may be substituted by radicals as described for R1 to R4, and where one or more of the substituents R1 to R4 may be a η5-phospholyl complex of the formula I bound via a further bridge, where M is selected from among Zr, W, Mn, Fe, Ru, Co, and L is selected from among cyclopentadienyl, CO, halogen and phosphine and mixtures thereof.
  2. A process as claimed in claim 1, wherein the η5-phospholyl complexes are selected from among the following structures, in which Ph is phenyl and Cy is cyclohexyl,
    Figure 00260001
    Figure 00260002
    Figure 00260003
    Figure 00260004
    Figure 00260005
  3. A complex of the formula (VI) M'L'n'(CO)m' where
    M'
    is rhodium,
    L'
    is a monodentate or polydentate η5-phospholyl complex ligand capable of complex formation as claimed in claim 1 or 2 or a mixture thereof,
    n'
    is at least 1,
    m'
    is at least 1.
  4. The use of a complex as claimed in claim 3 as catalyst in the hydroformylation of olefins.
EP00935014A 1999-05-12 2000-05-12 Eta 5-phospholyl complexes and their use in hydroformylation Expired - Lifetime EP1178951B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19921730A DE19921730A1 (en) 1999-05-12 1999-05-12 Aldehyde preparation by hydroformylation of olefins uses (new) sub-group VIII catalysts with phospholyl or polyphospholyl complexing ligands, also useful in olefin hydrocyanation
DE19921730 1999-05-12
PCT/EP2000/004322 WO2000069801A1 (en) 1999-05-12 2000-05-12 Eta 5-phospholyl complexes and eta 5-polyphospholyl complexes and their use in hydroformylation

Publications (2)

Publication Number Publication Date
EP1178951A1 EP1178951A1 (en) 2002-02-13
EP1178951B1 true EP1178951B1 (en) 2003-04-16

Family

ID=7907734

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00935014A Expired - Lifetime EP1178951B1 (en) 1999-05-12 2000-05-12 Eta 5-phospholyl complexes and their use in hydroformylation

Country Status (3)

Country Link
EP (1) EP1178951B1 (en)
DE (2) DE19921730A1 (en)
WO (1) WO2000069801A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10033982A1 (en) * 2000-07-13 2002-01-24 Basf Ag Process for the preparation of addition products of ethylenically unsaturated compounds
FR2820137B1 (en) * 2001-01-26 2005-12-23 Atofina BIPHOSPHOLES BRIDGES AND METALLOCENES PREPARED THEREFROM
SG11201807445TA (en) 2016-03-01 2018-09-27 Kuraray Co Method of producing dialdehyde compound

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1458029A (en) * 1964-12-14 1966-11-04 Shell Int Research Process for preparing aldehydes and alcohols
DE19621967A1 (en) * 1996-05-31 1997-12-04 Basf Ag Process for hydroformylation and suitable catalysts which contain phosphorus compounds as ligands

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DILLON, K.B.; MATHEY, F.; NIXON, J.F.: "TAU-COORDINATION COMPLEXES", PHOSPHOROUS: THE CARBON COPY, XX, XX, 1 January 1998 (1998-01-01), XX, pages 258 - 358, XP000996501 *
GANTER C, GLINSBOECKEL C, GANTER B: "NEW P,N-CHELATE LIGANDS BASED ON PYRIDYL-SUBSTITUTED PHOSPHAFERROCENES", EUROPEAN JOURNAL OF INORGANIC CHEMISTRY - CHEMISCHE BERICHTE, WILEY-VCH VERLAG, WEINHEIM., DE, vol. 08, 1 January 1998 (1998-01-01), DE, pages 1163 - 1168, XP000996198, ISSN: 1434-1948, DOI: 10.1002/(SICI)1099-0682(199808)1998:8<1163::AID-EJIC1163>3.0.CO;2-P *

Also Published As

Publication number Publication date
EP1178951A1 (en) 2002-02-13
WO2000069801A1 (en) 2000-11-23
DE19921730A1 (en) 2000-11-16
DE50001801D1 (en) 2003-05-22

Similar Documents

Publication Publication Date Title
EP2091958B1 (en) Bisphosphite ligands for hydroformylation catalyzed by transition metals
EP3070093B1 (en) Novel organophosphorus compounds based on anthracentriol
DE19810794A1 (en) Catalyst useful for hydroformylation of ethylenically unsaturated compounds to produce aldehydes
EP1257361B1 (en) Phosphorous, arsenic and antimony compounds based on diaryl-anellated bicyclo[2.2.n] parent substances and catalysts containing same
EP0435084A1 (en) Process for the production of aldehydes
DE10313319A1 (en) Hydroformylation process
EP1296992B1 (en) Phosphacyclohexanes and the use thereof in the hydroformylation of olefins
DE60132242T2 (en) PHOSPHONITE LIGANDS, CATALYST COMPOSITIONS AND THEIR USE IN HYDROFORMYLATION PROCESS
WO2002022261A2 (en) Method for hydroformylation using catalysts of xanthene-bridged ligands
DE19838742A1 (en) Valeraldehyde and process for its preparation
EP0906261B1 (en) Hydroformylation process and catalysts suitable therefor containing phosphorus compounds as ligands
EP0491239B1 (en) Process for the preparation of aldehydes
EP0811424A2 (en) Catalyst systems based on Rhodium complexes with diphosphine ligands and their use for the preparation of aldehydes
EP1178951B1 (en) Eta 5-phospholyl complexes and their use in hydroformylation
DE19964298C2 (en) Preparation of substituted arylhalophosphines for use in tertiary phosphine ligand catalysis
DE69411005T2 (en) METHOD FOR PRODUCING RIGHT-CHAIN ORGANIC ALDEHYDE COMPOUNDS
EP1273564B1 (en) Process for the preparation of aldehydes
EP1161437B1 (en) Phosphabenzene compounds and their use as ligands for hydroformylation catalysts
EP1025111B1 (en) Method for producing phosphabenzene compounds
DE4426577C2 (en) Process for the hydroformylation of olefinically unsaturated compounds
EP3296304B1 (en) Monophosphites with methylene-bridged diphenol and anthracenyl remnant
DE10033982A1 (en) Process for the preparation of addition products of ethylenically unsaturated compounds
DE10133072A1 (en) Production of aldehydes by hydroformylating olefinically unsaturated compounds using a rhodium catalyst comprises adding extra rhodium in preformed catalyst form
DE4217803A1 (en) New sulphonated 2,2&#39;-bis:di:phenyl-phosphino-methyl-1,1-di:naphthyl cpds.
DE102005019237A1 (en) Process for the hydroformylation of substituted allylbenzenes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20011206

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20020207

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RIC1 Information provided on ipc code assigned before grant

Free format text: 7C 07C 45/50 A, 7C 07F 17/00 B, 7C 07F 17/02 B, 7B 01J 31/20 B, 7B 01J 31/18 B, 7B 01J 31/22 B, 7B 01J 31/24 B

RTI1 Title (correction)

Free format text: ETA 5-PHOSPHOLYL COMPLEXES AND THEIR USE IN HYDROFORMYLATION

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE

REF Corresponds to:

Ref document number: 50001801

Country of ref document: DE

Date of ref document: 20030522

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

Ref document number: 1178951E

Country of ref document: IE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040119

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100730

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50001801

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50001801

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111130